Polybasic acid-polyhydric alcohol esters and polymers thereof



Patented Sept. 4, 1945 ronmslc ACID-POLYHYDRIC ALCOHOL Es'rEBs AND ronrmms manor Irving E. Muskat and Akron,

Franklin Strain, Ohio, asslgnors to Pittsburgh Plate Glass Company, Allegheny County, Pa., a corporation of Pennsylvania No Drawing. Application October-15, 1940,,

. Serial N 0. 361,283

'8 Claims.

This invention relates to novel compositions, polymers of such compositions and methods of preparing such polymers. In accordance with the present invention we have prepared a novel class of complex mixed esters of polyhydric compounds such as glycerol, giycols, polyglycols, polyglycer- 013, etc., and acid esters of carbonic acid and unsaturated alcohols.

t especial interest are the esters of glycerol, alkylene glycols such as ethylene glycol, or the polyethylene glycols such as di-, tri-, or tetraethylene glycol, propylene glycol, butylene glycol, isobutylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, or other glycol or polyglycol such as trimethylene glycol, pentamethylene glycol, pinacol, tetramethylene glycol, alpha methyl tetramethylene glycol, alpha methyl pentamethylene glycol, octamethylene glycol, monomethylene glycol, 1,3-xylene alcohol decamethylene glycol, etc. Esters of other polyhydric compounds such as methyl gh'cerol, erythritol, pentaerythritol, polyglycerols, sorbitol, mannitol, halohydrins, such as glycerol monochlorhydrin, resorclnol, pyrogallol, polyhydroxy benzene, polyhydroxy anthracene, polyhydroxy naphthalene, starch, sugar, phthalyl alcohol, 1,4-dihydrocyclohexane, 1,4-dioxanediol-2,3; polyvinyl or polyallyl or other polymerized alcohol, cellulose, cellulose hydrate, cellulose monoacetate, cellulose diacetate, cellulose mono or dibutyrate or similar cellulose esters or ethers such as mono or diethyl, methyl or benzyl cellulose may also be prepared.

The invention is particularly applicable to the formation of the unsaturated alcohols containing up to carbon atoms. such as, allyl, metha-llyl, crotyl, 2-chloroallyl, chlorocrotyl, ethylallyl, cinnamyl, propargyl, methyl vinyl carbinyl or other lower unsaturated alcohol particularly alcohols capable of forming polymerlzable esters.

In the preparation of carbonate esters herein contemplated high yields may be obtained by reaction of an unsaturated chloroformatle such as allyl, methallyl, crotyl, or similar chloroformate with a polyhydric alcohol. Likewise similar esters may be prepared by forming the polychlorofor-mate of glycol, glycerol or similar compound and treating with an unsaturated alcohol. Thus allyl chloroiormate may be formed for example by passing gaseous phosgene through allyl alcohol. Thereafter the excess alcohol and "other impuri-- ties may be removed by washing the chloroformate with water and drying by means of suitable dehydrating agents suchas calcium chloride.

This chlorotormate may then be reacted with calcium, magnesium or barium hydroxideor other alkaline agent capable of removing HC1 which may otherwise accumulate during the reaction. This esterification may be conducted in an aqueous or nonaqueous media, preferably in an organic solvent such as acetone, pyridine, dioxane, etc.

Alternatively the corresponding polychloroformate of a. polyhydroxy compound may be prepared by treatment of such materials with phosgene. Thus glycohglycerol, diethylene glycol, hydrated cellulose, etc. may be treated to form polychloroformates. These chloroformates may then be'treated with unsaturated alcohols in the presence of an alkaline agent'to form the corresponding esters.

The compositions herein described vary from high boiling point liquids to solids. Many of the liquids are very clear and colorless and are miscible with numerous organic solvents such as acetone, alcohol, chloroform, dioxane, benzene, toluene, xylene, ethyl ether, 'paraflin hydrocarbons, etc.

These compositions may be used for many purposes such as solvents, paint compositions, pharmaceuticals, plasticizers, etc. for various materials such as cellulose, vinyl, urea, phenol, acrylic or styrene resins or plastics. In particular, the products are found to polymerize in the pressure of catalysts, such as heat, light, oxygen,- ozone, peroxides such as lauryl or benzoyl peroxide, etc., to form products of desirable character. 1

By polymerization of these compounds it is pos sible to secure a wide range of polymers. some of which are extremely hard, while others are soft, flexible and often rubber-like in character. In general, the polymers thus obtained are transparent and colorless, although the polymer occasionally may be slightly yellow. If desired, the compounds herein described may be cast polymerized to form products having various shapes. These polymers in their finally cured state are substantially infusible and insoluble, and in general, are substantially unaffected by acids, alkalies, water or organic solvents.

In accordance with the present invention, intermediate polymers which are fusible or thermoplastic also may be prepared. In general, such polymers are soluble in various organic solvents such as acetone, carbon tetrachloride, benzene, xylene, toluene, dioxane, etc.- These fusible polymers may be further polymerized to aniniuslble state to fol-ii products similar to the infusible polymers mentioned above. Thus, the fusible polymer may be molded or otherwise shaped and polymerized by means of heat and/or light to are obtainable by this means.

The fusible polymers herein described may be prepared by polymerizing the unsaturated compounds which contain at least two polymerizable unsaturated groups until substantial polymerization has occurred and interrupting polymerization before the polymer is converted into a geliIt is found that when polymerization of these materials is initiated, a fusible polymer is preliminarily formed. As polymerization proceeds, the monomerpolymer mixture'is converted into a gel which is substantially infusible. This polymer does not fuse at atmospheric pressure. Further polymerization hardens the polymer to its final state of polymerization. By interrupting the polymerization, it is possible to remove a portion or all of the monomer and to recover the fusible polymer substantially free from monomer oi at least as a concentrate containing substantially less monomer than 3s present in the monomer-polymer mixture formed by ordinary polymerization of undiluted monomer. interruption of polymerization may be effected by cooling. addition of inhibitors or by other methods as hereinafter more fully described.

The methodof securing the fusible polymer is dependent upon thenature of the materialwhich is undergoing polymerization. In general; it is possiblet'o secure'the fusible material in superior yields by polymerizing the-monomer in a solu- -tion in which the fusible polymer is normally soluble. This polymer is generally soluble in the solvents whichare capable of dissolving the usual thermoplastic vinyl or acrylic resins such as polymethyl methacrylate or polyvinyl acetate.

Thus, such solvents'as acetone, dioxane, chloroform, toluene, benzene, carbon tetrachloride, methyl Cellosolve acetate, phenyl Cellosolve, dichlorethyl ether, xylene, tetralin, dibutyl phthalate, trichlorethylene, tetrachloroethane, etc., or mixtures of these solvents generally are found to be suitable. Solutions having concentrations of to 60 percent of monomer yield satisfactory products.

In each case, th polymerization may be interrupted before the infusible product is produced. This may be accomplished by stopping polymerization as the mixture ofmonomer and polymer begins to srow'viscous and before infusible gel formation occurs. In accordance with one illustrative method of interrupting polymerization, the polymer may be separated from the tion may also be halted by lowering the temperature of thereaction mixture to a suitable degree, for example, to room temperature or below.

In accordance with another effective method of interrupting polymerization, inhibitors, such as pyrosallol, hydroquinone, aniline, phenylene diamine, sulphur, thiophenol, organic or inorganic salts or complexes of the reduced forms of metals such as copper, manganese, cobalt, nickel, etc. may be added to the polymer during polymerization or before polymerization has been initiated. When the fusible polymer is produced in solution, it 'may be recovered by methods other than by treatmentv with a nonsolvent, such as by slow evaporation or distillation of the solvent. These fusible polymers maybe extruded, molded, shaped, or otherwise worked into desirable forms and after flnal shaping, the products may be completely hardened and rendered infusible by suitable methods hereinafter more fully set forth.

In polymerizing the compounds herein contemplated, the time required in order to initiate polymerization and to secure a fusible polymer This monomer by convenient methods, for example,

by the addition of a compound in which the .poLvmers are normally insoluble, such as methyl or ethyl alcohol, petroleum ether, water, ethylene glycol, etc. This processpermits the isolation of the fusible polymer in a. substantially pure state and is particularly adapted to use when the material ispolymerized in solution. Polymerizavaries widely in view of slight traces of peroxides 'or inhibitor which may be present. For this reason, the viscosity of the composition undergoing polymerization is observed and, in general, polymerization is interrupted after the viscosity of the composition has approximately doubled- In many cases, subjection of the compound to polymerization conditions for a period of one-half to two hours is sunicient, although some compounds polymerize somewhat more slowly.

Generally, it is preferred to conduct the polymerization in solution in order to secure improved yields, Thus, it is found that the presence of a solvent substantially improves the yield of fusible polymer. Likewise, addition of inhibitor may improve yields although in such a case the rate of polymerization is comparatively slow.

It is also possible to produce the fusible polymer in accordance with ourinvention without resorting to the use of solutions of the monomer, although the yield of polymer is, in general, somewhat, lower than when a solvent is present. Thus, the monomer may be polymerized directly by use of heat and/or light, preferably in the presence of catalysts, such as air, ozone, oxygen,

peroxides, and the like, and interrupting polymerization at the proper time. Since the polymerization 'may proceed without undue rapidity, with; many of these materials, the reaction may be stopped before the infusible gel state is reached without difliculty, either by use of inhibitors or by cooling as hereinbefore mentioned.

The fusible polymer so produced may be molded to any desired shape and subsequently cured to the infusible state. In treating materials which polymerize slowly, it is found that if considerable monomer is retained by the polymer, upon 03.111118, considerable difiiculty is encountered in securing complete or substantially complete polymerization of the residual monomer. This may be undesirable. Accordingly, we have found that in most cases it is desirable to remove all or a portion of such monomers from the polymer prior to curing the polymer to its infusible state.

Similarly, the monomer may be extracted with a'solvent in which the polymer is insoluble such as methyl or ethyl alcohol. Additionally, the polymer and monomer may be separated bydissolving the product in a solvent for both monomer and polymers and adding a nonsolvent to 'pre-' cipitate the fusible polymer.-

The selection of a'solvent in which to conduct polymerization .or a nonsolvent with which to precipitate polymer is dependent upon the nature of the material undergoing p l m risation. Withsuch materials as the ethylene glycol bis (allyl carbonate) and similar glycol esters of the u saturated alcohol acid. esters of polybasic acids,

carbonate esters such as glycol bis '(allyl car- 25 ,catalysts .or by catalysts previously introduced.

bonate), polymerization in solution for a period of 17 hours is found to be satisfactory when the temperature is 60' C. This period must be materially shortened with rising temperature and at 100 C. it is found that the fusible polymer must be recovered within a few minutes after the polymerization reaction is initiated. Similar variations of time of polymerization in accordance with the temperature is found necessary in treating other polymerizable materials. In any case, however, the polymer is preferably recovered by interrupting polymerization as the monomer undergoing treatment grows viscous since after solidification thereof the polymer may be foun to be substantially insoluble. 1

The fusible polymers so produced have many characteristics which are similar to those of usual thermoplastic polymers. They are generally soluble in such organic solvents as acetone, dioxane, benzene, toluene, chloroform, ethyl Cellosolve acetate, triacetin, phenyl Cellosolve, etc.,

and soften or flow upon heating under atmospheric pressure. They are precipitated from solutions by use of nonsolvents as white amorphous powder v m nets may be secured by increasing the catalyst or as plastic semi-liquid resins.

In accordance with our'invention, we have found that upon subjection of these polymers to heating at temperatures somewhat above the softening point thereof, for a'sufilcient period of time, they are converted into ihfusible, insoluble; transparent hard and wear-resistant products. This conversion may be assisted by the incorporation of usual polymerization catalysts, such 'as oxygen, ozone, air, peroxides, such as hydrogen peroxide, or benzoyl peroxide, basic or acidic catalysts, light, etc. By use of catalysts, it is found that the conversion of these products to theinfusible state may be secured at lower temperatures. In order to secure transparent uniform products the polymerization should be controlled to permit the polymer to flow together, or if desired, to become completely molten prior to corrverting the polymer to its infusible state. The application of superatmospheric pressure assists the production of satisfactory producta, I

By operating in accordance with the invention, it is thus possible to form a mo] article from the fusible polymer such as the ble polymeric, ethylene glycol bis (allyl bonate), ethylene glycol bis (methallyl carbonate), or other products previously referred gto,

and thereafter, to render the molded products insoluble and infusible by heat. In this manner we are able to prepare transparent, hard. infusi ble molded products which have many of the dea sirable properties of the conventionally known thermoplastic resins as well. By pr ll r'regm lation of the pressure and temperature. the fusible polymer may be extruded under suchconditions that it becomes infusible as it leaves the extrusion die.

Since the fusible polymer is a truethermoplastic. it often may be kept in the molten state for an indefinite period, particularly by incor 'porating an inhibitor such as hydroquinone,

Io whereby conversion to the infusible state may be prevented. Likewise, polymerization may be delayed to such an extent thatmolten products may be obtained prior to polymerization by utilining mixtures .of catalysts and inhibitors. It

20 is thus possible to form cast or molded products In some cases, polymerization of such products may be assisted by heating the molded or cast material in a molten or solid state in the presence of air, peroxides, etc. In accordance with a fur- 30 ther modification, the cast or molded thermoplastic polymer maybe coated with a solution of catalyst or a film of monomer or a solution of fusible polymer which contains high catalyst concentration may be applied to the surface of the 35 molded product. Heat. pressure, and/or ultraviolet light may be utilized to mer to the infui'dble state.

In additionx'it is possible to efi'ect a conversion of the exterior of the plastic without completely convert the polyconverting the interior thereof to the infusible,

insoluble state. Thus; cast or molded products, made from the fusible polymers herein described may be subjected to local surface heating whereby the surface is converted without complete con-. version of the interior. In this manner, it is possible to secure integral products po a great flexibility and resiliency, the surfaces of which are extremely hard and insoluble. Similar prodfiexible gel due to the presence of added plasticizer.

A large number of inert substances may be incorporated with the fusible polymer before sub- Jecting the molding condition. Suitable for such purposes are: plasticizers, softening agents or fillers, such as dlbutyl' phthalate, dicyclohexyl phthalate, triacetin, tricresyl phosphate, natural or synthetic-resins, pigments, including titanium dioxide, carbon black, chromic oxide, lead chromate, etc., and organic dyestufis, such as methylene blue, methyl orange, etc.

If desired, imilar products may be made from suitable copolymers, for example, ethylene glycol bis (allyl carbonate) or similar estermay be copolymerized with other compatible polymerizable materials such a'sacrylates or alpha-substituted acrylates, for example, methyl, allyl or ence may be secured by impregnating flbrous' sheets of paper, linen, canvas, etc. with the monomer or polymer herein described, forming a laminated product, and curing the same to an infusible state.

Leather, paper, wood or other comparatively porous substances may be steeped in a solution of the fusible polymer or a molten body thereof, and one or more layers heated under pressure, generally in the presence of catalyst to convert the absorbed polymer to the infusible, insoluble form. Greatly improved products, particularly in regard to strength, water-proofing and electrical properties are obtained.

The polymers which we have prepared are capable of numerous uses such as in lacquers, or other coating compositions, molded articles, safety glass, etc. Where the composition is used for coating, it may be applied insolution or in solid form, either alone or in combination with natural or synthetic drying oils or resins and the like, the solvent removed and the coated arascent v 1 temperature below about 15 to 20 C. After phosgene in the proportion of about 0.9 mole of phosgene per mole of allyl alcohol had been intmduced, the mixture was allowed to stand for one hour. Thereafter, the reaction mixture was washed with water to remove unreacted allyl alcohol and dried over calcium chloride.

2.2 moles of allyl chloroformate was added dropwise to a solution of one mol of ethylene glycol in 2.4 moles of pyridine while cooling the reaction mixture to a temperature of 10 to 15 C. After the chloroformate had been added, the mixture was allowed to stand at room temperature for about onehour. The product was diluted with water, washed with dilute HCl solution and then with sodium chloride solution until the product was neutral. Thereafter, the product was washed with water and dried over calcium chloride. The ethylene glycol bis(al lyl carbonate) having a boiling point of about 118-122 C. at 1 mm., an index of refraction of about (N 1.4443, a density of (114") about 1.114, and having the probable formula was obtained. Example II Phosgene was bubbled into-a flask containing genepermoleof methallyl alcohol had been introticle baked to render the surface infusible. In

this manner, it is possible to surface other polymers which are less resistant to the action of solvents or of heat. When a coating ofthe fusible polymer of the compounds herein contemplated is deposited upon polymerized methyl methacrylate or similar polymer and the solvent removed, a coherent surface thereof is formed. Upon heating the coated article to suitabl temperatures, this surface may be made transparent, hard. and infusible.

40 refraction at 20 c. of 1.427 and a boiling point Being of the thermosetting type, these resins do not exhibit the phenomenon of cold flow".

and are thus especially desirable for such uses as airplane Windshields, where the pressure differences have been found to bow thermoplastic glass substitutes, particularly at the higher altitudes. Coatings may be applied to metal, glass, wood, synthetic resins, etc. surfaces by extrusion of the heated fusible polymer directly on the suitably-prepared surface. In similar manner, the surface may be heated and the polymer applied in powdered form, whereupon fusion occurs, first to give a smooth, homogeneous film which may then be heat-hardened.

The process may also be extended to the proof approximately 130 C. at atmospheric pressure.

2.2 moles of methallyl chloroformate was added dropwise to a solution of one mole of ethylene glycol in 2.4 moles of pyridine while cooling the reaction mixture to a temperature of 10to 15 C. After the chloroformate had been added, the mixture was allowed to stand at room temperature for about one hour. The product was di-.,

luted with water, washed with dilute HCl'solution duction of mixed polymers or copolymers. Thus,

. Example I Phosgene was bubbled into a flask containing 'allyl alcohol at a rate of 20 milliomoles per mina and then with sodium chloride solution until the product was neutral. Thereafter, the product was recovered and dried over calcium chloride."

The ethylene glycol bis(methallyl carbonate) obtained was a colorless liquid which boiled at 142 C. at 2mm. in a slow stream of carbon dioxide and had a density of about 1.110 and an index of refraction (N of about 1.4490. The probable formula of this compound was as follows:

7.3 moles of allyl chloroformate was added dropwise to a solution of 3.3 moles of triethylene glycol} in 8 moles of pyridinewhile cooling the reactigm mixture to a temperature of 10 to 15 C. After the chloroforfnate had been added, the

was allowed tostand atroom temperature'fiorabout an hour and the ester washed and recovered in Example I. The triethylene glycol bis(a, l carbonate) obtained was a colorless ute while agitating the mixtureand cooling to a 76 liquid which had an index of refraction (N P) of assent vene glycol in lieu of ethylene glycol. The ester thussecuredwasacolorlessliduidwhichhadan and dried over calcium chloride. wherebythe dichlorotormateoiethyleneglycolwasobtained.

Thiscompoundwasacolorlessliquidhavinga 20C. p 4 4%.) or 1.456. l'a:ample x1 index of refraction (N 01' about 1.454, a density of 1.133 at 25' C. P0 of the material occurred when distillation was attempted at 2 mm. pressure. trample v The process described in Example I was repeated using an equivalent amount of diethylene glycol in lieu oi ethylene glycol. The ester thus obtained was a colorless liquid which had an index of refraction or 1.449 at 0., a density of about 1.133 at 20 C./4 C. and a boiling point of about 166 C. at 2 mm. pressure.

Emmpls VI The process of Example IV was repeated using an equivalent amount or methallyl alcohol in lieu of allyl alcohol. The methallyl ester thus produced was a colorless high boiling liquid which polymerized when distillation was attempted at 2 mm. pressure.

Example W:

The process of Example III was repeated using an equivalent amount of metballyl alcohol in lieu of allyl alcohol. The triethyl'ene glycol bis(methallyl carbonate) obtained was a colorless high boiling liquid which polymerised when distillation was attempted at 2 mm. pressure.

Example VIII The process of Example V was repeated using an equivalent amount of methallyl alcohol in lieu of allyl alcohol. The diethylene glycol bis- (methallyl carbonate) obtained was a colorless liquid having a refractive index at 20 C. of about 1.453, a density v 20C. 4C. 01 about 1.114.

Emmple IX 95 parts of allyl salicylate was dissolved in 250 parts of acetone and 22 parts of sodium hydroxide dissolved in water was slowly added. During this addition, a stream of phosgene was passed into the solution and the temperature of the solution was maintained below about 15 C. The re- A action mixture was diluted with cold wate and the solid carbonate precipitated. This ester was washed withwater and recrystallized from alcohol. It possessed a melting point of 5l-53 C. The product was the carbonate diester of allyl salicylate.

. Erample. X 4

25 moles of phosgene was passed into 10 moles of ethylene glycol at a rate of 100 millimoles per minute and at a temperature below about 20 C. The reaction mixture was warmed to C. and evacuated for several minutes by means ot a vacuum pump to remove excess pho'sgene. The reaction mixturewas washedtour times with water 25 moles of. phosgene was introduced into 10 moles or diethylene glycol and the product washedasinExamplelwherebythedichloroiormate or diethylene glycol was prepared ins: percent yield. This compound was a colorless liquid. y p

Example x11 7.2 moles oi! allyl chlororormate was added dropwisetoasolutionoi2molesoiglycerinein 7.8. moles of pyridine while cooling the reaction mixture to a temperature of 10 to 16 C. After the chlorgiormate had been added, the mixture was allowed to stand at room temperature (or about minutes. The products werewashed with water and recovered as in Example I. The glycerol tris allyl carbonate) thus obtained was a colorless liquid having an index 01' retraction (N of about 1.4558, and a density (114") 01 about 1.194. The probable formula or this pound is:

: o m-o- -ocmom-cm Example XIII 2.79 moles of diethylene glycol bis dichloroi'ormate was added slowly to 6.14 moles of 2-chlorallyl alcohol dissolved in 8.! moles of pyridine.

The reaction mixture was washed and purified J as in Example I. The product obtained, di-

' ethylene glycol bis (z-chlorallyl carbonate),'was

a colorless liquid which possessed an index of refraction (N or about 1.472 and a density or.

(d4') of about 1.30.

' Example XIV 4 moles of allyl chloroiormate was slowly added to a dispersimi of 2 moles of ethylene diamine in 50 percent aqueous sodium hydroxide solution containing 4 moles 01' NaOH. A substantial quantity of nonhygroscopic white crystals was formed. These crystals were filtered and dried.

The product melted at 81-84 C. and was readily soluble in dioxane and acetone. When heated with 5 percent benzoyl' peroxide, 9. hard, yellow, translucent polymer was obtained.

Example XV 365 parts by weight of allyl chlorofonnate was added, over a period of two and one-half hours, to 357 parts by weight of allyl lactate dispersed in- 268, cc. of pyridine with stirring and at a temperature of 2 to 18 C. The reaction mixture was acidified to the methyl orange endpoint,

washed with water, dilute hydrochloric acid, di-

lute aqueous sodium carbonate solution. again with. water, and was finally dried over anhydrous sodium carbonate. The product was thereafter purified by distillation. This product boiled at about 112 C. at a pressure of 2 mm. 01' mercury com- 1 remove "volatile impurities.

Example XV I 12.1 parts by weight of allyl chloroiormate was slowly added to 16.4 parts by weight of castor oil in the presence of a large excess of pyridine.

The product was washed successively with water, dilute hydrochloric acid and then with water. Thereai'ter, the product was heated to 100 C, to

The product obtained was a liquid which was soluble in. petroleum ether.

Example XVII Phosgene was bubbled into a flask containing a solution containing 1690 grams of allyl lactate per liter of pyridine at a rate or 20 millimoles per minute while agitating the mixture and cooling to a temperature below about 15 to 20 C.

- heated, with s ,at80to85C.untilthe viscosity had increased noticeably. Thereafter. the mixture was cooled and methanol was added to the point of turbidity. It was then added to volumes of methanol with vigorous stirring.

' The polymer was separated by decantation, dissolved in acetone, reprecipitated with methanol tained.

After phosgene in the proportion of about 0.5

mole of phosgene per mole of allyl lactate had been introduced, the mixture. was allowed to stand for one hour. Thereafter, the reaction mixture was acidified'to the methyl orange endpoint and washed successively with equal volumes of water, dilute hydrochloric acid and dilute aqueous sodium hydroxide, and finally twice with water. The product was a colorless liquid which boiled at about 154 C. at a pressure of 4 mm.

1 of mercury, and had a. density (124) of 1.22 and an index of refraction (N or about 1.447.

Example XVIII Phosgene was bubbled into a flask containing one mole of allyl Cellosolve per 1.2 moles of pin dine at a rate of 18 millimoles per minute while agitating the mixture and cooling to a temperature below about 15 to 20 C. After phosgene in the proportion of about 0.45 mole of phosgene per mole of allyl alcohol had been introduced, the mixture was. allowed to stand for one hour. Thereafter, the reaction mixture was extracted with ether and the ether extract washed with dilute hydrochloric acid, ammonium hydroxide, dilute hydrochloric acid and finally, with satura'ted sodium chloride solution.

The ester, bis(2-al1yloxyethyl) carbonate thus obtained was a colorless liquid at 133 to 140 C. at 4 mm. pressure and a retractive index (N of about 1.455 and a density (114) or about 1.053.

Example XIX One mole of allyl chloroformate was added dropwise to a solution of 1.1 mole of allyl Cellosolve in 1.2 moles of pyridine, while cooling the reaction mixture to a temperature of below 10 C. After the chloroformate had been added, the

- mixture was allowed to stand at room temperature for about an hour. The product was washed and recovered as in Example I. Thereafter, the,

" Example XX A quantity of ethylene glycol bis(allyl carbonate) prepared as in Example I, was dissolved in an equal weight of dioxane and 4 percent benzoyl peroxide on the basis of the-weight of the monomer was introduced. The solution was Example XXI A quantity of diethylene glycol bis(a1ly1 carbonate) prepared as in Example V, was dissolved inan equal weight of dioxane and 4 percent benzoyl peroxide on the basis of the weight of the polymer was introduced. The solution was heated, with stirring, at .80 to 85 C. until the viscosity doubled. Thereafter, the mixture was cooledand methanol was added to the point of turbidity. It was then added to 5 volumes or methanol with vigorous stirring. The polymer was separated by decantation, dissolved in acetone,,reprecipitated with methanol and again recovered. The polymer was then dried under subatmospheric pressure to constant weight. A white fusible polymer was obtained. A quantity 01' this polymer was mixed with 5 percent benzoyl p roxide, placed in a mold and heat to 150 C., under a pressure or 2000 lbs. per sq. in. for 20 minutes. A transparent sheet of infusible, insoluble polymer was obtained.

Example XXII A quantity of ethylene glycol bis(methallyl carbonate) prepared as in Example II was dissolved in an equal weight of dioxane and 4 percent benzoyl peroxide on the basis of the weight oi the polymer was introduced. The solution was heated, with stirring, at to- C. until the viscosity doubled. Thereafter, the mixture was cooled and methanol was added to the point of turbidity. It was then added to 5 volumes of methanol with vigorous stirring. The polymer was separated by decantation, dissolved in. acetone, reprecipitated with methanol and again recovered. The polymer was then dried under subatmospheric pressure to constant weight. A white fusible polymer was obtained. A quantity of this polymer was mixed with 5 percent benzoyl peroxide, placed in a mold and heated to C. under a pressure of 2000 pounds per square inch for 20 minutes. A colorless sheet of infusible, insoluble polymer was obtained.

Example XXIII A quantity of diethylene glycol bls metha1lyl carbonate) prepared as in Example V111, was dissolved in an equal weight of dioxane and 4 percent benzoyl peroxide on the basis of the weight or the polymer was introduced. The solution was heated, with stirring, at 80 .to 85 C. until the viscosity doubled. Thereafter, the mixture was cooledand methanol was added to the point of turbidity. It was then added to 5 volumes of methanol with vigorous stirring. The polymer was separated by decantation, dissolved in ace: tone," reprecipitated with methanol and asaln recovered. The polymer was then dried under subatmospheric pressure to constant weight. A white gummy mass was obtained. A quantity of this polymer was mixed with one. percent benzoyl peroxide, placed in a mold and heated to 150 C. under a pressure of 2000 pounds per square inch for 20 minutes. A colorless sheet of infusible, insoluble polymer was obtained.

Example xxzv 2. quantity of polyvinyl alcohol was dissolved by heating with about 10 timesits weight oi. pyridine for 16 hours at 85C. The solution was cooled to about C. and mixed with cold allyl chloroiormate while maintaining the temperature at to '7 C. The mixture was stirred,

certain embodiments thereof, it is not intended that such details shall be regarded as limitations upon the scope of the invention, except insofar as included in the accompanying claims; The term "poly in the claims is intended to refer to the degree of esterification of. the alcohol and is not intendedto refer to polymerization.

We claim:

1. Ethylene glycol bis(allyl carbonate).

2. Ethylene glycol bis(methallyl carbonate).

3. A polymer of ethylene-glycol bis(allyl carbonate).

4. A polymer 0!. ethylene glycol bis(methallyl carbonate). g "r" 5. Ethylene glycol bis(chloroallyl carbonate) 6. A polymer of ethylene alcohol bis(chloroallyl carbonate).

7. An ethylene glycol bis(alkenyl carbonate) wherein the alkenyl radical contains an oleflnic linkage between the second and third carbon atoms from the carbonate radical.

8. A polymer of a compound defined in claim '1.

IRVING E. MUSKAT. FRANKLIN STRAIN. 

